Resin composition, copper clad laminate and printed circuit board using same

ABSTRACT

The present invention provides a resin composition comprising: (A) 100 parts by weight of epoxy resin; (B) from 10 to 80 parts by weight of benzoxazine resin; (C) from 10 to 50 parts by weight of dicyclopentadiene phenol resin; and (D) from 0.5 to 5 parts by weight of amine hardener; wherein the resin composition is free of diallyl bisphenol A (DABPA).

TECHNICAL FIELD

The present invention relates to a resin composition, particularlyrelates to a resin composition used for copper clad laminates andprinted circuit boards.

BACKGROUND

It is known in the art that DICY has the disadvantages of low Tg andpoor heat resistance of laminate (measured by DSC, Tg=140° C.) duringPCT when it is used as a hardening agent for epoxy resin.

It is known in the art that Benzoxazine (Bz) resin is used as ahardening agent for epoxy resin. But Benzoxazine resin requires aco-hardening agent to open the benzoxazine ring and then crosslink withan epoxy resin. CN1088727C by HITACHI KASEI IND CO LTD teaches thesynergistic effect of phenolic resin and Bz resin. However, the use ofphenolic resin results in too high dielectric properties (Dk about 4.4,Df about 0.014@2 GHz) and is impossible to meet the regulationrequirement of a low dielectric copper clad laminate.

In order to attain low dielectric properties of a copper clad laminate(D≦4.1, Df≦0.01@2 GHz). In the prior art people generally uses expensivecyanate ester resins. The cost of the material for making cyanate esterresins is about more than 8 times of epoxy resin. Thus the product isnot competitive due to high cost.

In summary, there is no resin composition that can attain low dielectricproperties and high laminate heat resistance without using cyanate esterresin in the art.

Therefore, there is an urgent need for a resin composition that canattain low dielectric properties and high laminate heat resistancewithout using cyanate ester resin.

SUMMARY OF THE INVENTION

The first object of the present invention is: in order to overcome thedisadvantage on cost, the present discloses a resin composition that canattain low dielectric properties and high laminate heat resistancewithout using cyanate ester resin.

The second object of the present invention is to provide a prepreg usingthe present resin composition.

The third object of the present invention is to provide a copper cladlaminate using the present resin composition.

The fourth object of the present invention is to provide a printedcircuit board using the present resin composition.

In the first aspect, the present invention provides a resin compositioncomprising:

(A) 100 parts by weight of epoxy resin;

(B) from 10 to 80 parts by weight of benzoxazine resin;

(C) from 10 to 50 parts by weight of dicyclopentadiene phenol resin; and

(D) from 0.5 to 5 parts by weight of amine hardener;

wherein the resin composition is free of diallyl bisphenol A (DABPA).

In an embodiment of the present invention, the dicyclopentadiene phenolresin is selected from the compound represented by the followingstructural formula:

wherein n is a positive integer from 1 to 5, Z is selected from —H, —CH₃or a combination thereof.

In an embodiment of the present invention, the amine hardener is atleast one selected from the group consisting of diamino diphenylsulfone,diamino diphenylmethane, diamino diphenyl ether, diamino diphenylsulfide and dicyandiamide.

In a preferred embodiment of the present invention, the amine hardeneris dicyandiamide (dicy).

In an embodiment of the present invention, the epoxy resin is at leastone selected from the group consisting of bisphenol A epoxy resin,bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol AD epoxyresin, bisphenol A novolac epoxy resin, o-cresol novolac epoxy resin,trifunctional epoxy resin, tetrafunctional epoxy resin,dicyclopentadiene type epoxy resin, DOPO-containing epoxy resin,DOPO-HQ-containing epoxy resin, p-xylene epoxy resin, naphthalene typeepoxy resin, benzopyran type epoxy resin, biphenyl novolac epoxy resin,isocyanate modified epoxy resin, phenol benzaldehyde epoxy resin andphenol aralkyl novolac epoxy resin.

In an embodiment of the present invention, the benzoxazine resin is atleast one selected from the group consisting of bisphenol A typebenzoxazine resin, bisphenol F type benzoxazine resin, diamino diphenylether type benzoxazine resin and phenolphthalein type benzoxazine resin.

In an embodiment of the present invention, the composition furthercomprises from 30 to 70 parts by weight of flame retardant, wherein theflame retardant is at least one selected from the halogen-free flameretardants and halogen flame retardants: bisphenol diphenyl phosphate,ammonium polyphosphate, hydroquinone-bis-(diphenyl phosphate), bisphenolA-bis-(diphenylphosphate), tris(2-carboxyethyl)phosphine,tris(isopropylchloro)phosphate, trimethyl phosphate, dimethyl methylphosphonate, resorcinol bis(dixylenyl phosphate), phosphazene,m-phenylene methylphosphonate, melamine polyphosphate, melaminecyanurate and tri-hydroxyethyl isocyanurate,9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO),DOPO-containing phenol resin, ethyl-bis(tetrabromophthalimide),ethane-1,2 bis(pentabromobenzene) and2,4,6-tris(2,4,6-tribromophenoxy)-1,3,5-triazine.

In an embodiment of the present invention, the flame retardant can bemixed with other components, or crosslinked to the epoxy resin ofcomponent (A) or other resins by a chemical method. For example,9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) can becrosslinked to the epoxy resin to form DOPO-containing epoxy resin.

The second aspect of the present invention provides a prepreg comprisingthe resin composition of the present invention.

The third aspect of the present invention provides a copper cladlaminate comprising the prepreg of the present invention.

The fourth aspect of the present invention provides a printed circuitboard comprising the copper clad laminate of the present invention.

DETAILED DESCRIPTION OF THE INVENTION

The inventors discover a resin composition that can attain lowdielectric properties and high laminate heat resistance without usingcyanate ester resins through extensive and intensive study. Thus, theamount of cyanate ester is reduced or even no cyanate ester is used. Theinventors complete the invention based on this study.

The present invention can meet the requirement of low dielectricproperties and high heat resistance without using cyanate ester resin inconsideration of reducing cost. But the present invention does notintent to exclude cyanate ester resin from the formulation.

As used herein, the terms “comprises,” “comprising,” “includes,”“including,” “has,” “having” and any other variation thereof areintended to cover a non-exclusive inclusion. For example, a compositionor article of manufacture that comprises a list of elements is notnecessarily limited to only those elements but may include otherelements not expressly listed or inherent to such composition or articleof manufacture. Therefore, the terms “comprises,” “comprising,”“includes,” “including,” “has,” and “having” indicate that variouscomponents may be used collectively in the mixture or composition ofthis invention. On the other hand, the terms “consisting essentially of”and “consisting of” include only the named components

as well as other non-essential components which do not significantlyaffect the uses and effects of the present invention.

The inventive concept of the present invention is that:

The present invention uses benzoxazine, dicyclopentadiene phenol resinand amine hardener as the hardening agent for epoxy resin and is free ofdiallyl bisphenol A. The resin composition of the present invention haslow dielectric properties and high laminate heat resistance due to thesynergistic effect between the epoxy resin and the three hardeners.

Hereinafter, the aspects of the present invention will be described indetail:

SUMMARY

The present invention provides a resin composition, which comprises:

(A) 100 parts by weight of epoxy resin;

(B) from 10 to 80 parts by weight of benzoxazine resin;

(C) from 10 to 50 parts by weight of dicyclopentadiene phenol resin; and

(D) from 0.5 to 5 parts by weight of amine hardener;

wherein the resin composition is free of diallyl bisphenol A (DABPA).

The present invention makes use of the synergistic effect among resincomponent (A) epoxy resin, resin component (B) benzoxazine resin, resincomponent (C) dicyclopentadiene phenol resin and resin component (D)amine hardener, thereby obtaining a resin composition having lowdielectric properties and high laminate heat resistance. The above resincomponents are required to comprise no diallyl bisphenol A (DABPA).Otherwise, the laminate heat resistance (T288) is likely to becomeworse.

Resin Component (A): Epoxy Resin

As mentioned above, the present application uses resin component (A)epoxy rein, the first hardener component (B) benzoxazine resin, thesecond hardener component (C) dicyclopentadiene phenol resin and thethird hardener component (D) amine hardener as the resin ingredients andmakes use of the synergistic effect among them to attain low dielectricproperties and high laminate heat resistance.

Generally, traditional epoxy resin is synergistic with other components.There should thus be no specific limitation to the epoxy resin so longas it will not limit the purpose of the present invention.

In the resin composition of the present invention, the component (A)epoxy resin is bisphenol A epoxy resin, bisphenol F epoxy resin,bisphenol S epoxy resin, bisphenol AD epoxy resin, bisphenol A novolacepoxy resin, o-cresol novolac epoxy resin, trifunctional epoxy resin,tetrafunctional epoxy resin, dicyclopentadiene type epoxy resin,DOPO-containing epoxy resin, DOPO-HQ-containing epoxy resin, p-xyleneepoxy resin, naphthalene type epoxy resin, benzopyran type epoxy resin,biphenyl novolac epoxy resin, isocyanate modified epoxy resin, phenolbenzaldehyde epoxy resin, phenol aralkyl novolac epoxy resin or thecombination thereof. DOPO epoxy resin can be DOPO-PN epoxy resin,DOPO-CNE epoxy resin, DOPO-BPN epoxy resin and DOPO-HQ epoxy resin canbe DOPO-HQ-PN epoxy resin, DOPO-HQ-CNE epoxy resin or DOPO-HQ-BPN epoxyresin.

The First Hardener: Component (B) Benzoxazine Resin

The present invention makes full use of the synergistic effect of thesethree hardeners. Particularly, in the resin composition of the presentinvention, the component (B) benzoxazine resin is bisphenol A typebenzoxazine resin, bisphenol F type benzoxazine resin, diamino diphenylether type benzoxazine resin, or phenolphthalein type benzoxazine resinor a combination thereof. More particularly, it is preferably at leastone selected from the following general formulas (1) to (3):

wherein X₁ and X₂ are each independently R or Ar or —SO₂—; wherein R isselected from —C(CH₃)₂—, —CH(CH₃)—, —CH₂— and unsubstituted orsubstituted dicyclopentadienyl; and Ar is selected from unsubstituted orsubstituted phenyl, biphenyl, naphthyl, phenolic aldehyde, bisphenol A,bisphenol A novolac, or bisphenol F functional groups. For example, thebenzoxazine resins are those commercially available from Huntsman underthe trade name LZ-8270, LZ-8280, LZ-8290, MT 35700, MT 35800.

In an embodiment of the present invention, the benzoxazine resin is atleast one selected from the group consisting of: bisphenol A typebenzoxazine resin, bisphenol F type benzoxazine resin, diamino diphenylether type benzoxazine resin and phenolphthalein type benzoxazine resin.

The resin composition of the present invention comprises from 10 to 80parts by weight of added benzoxazine resin based on 100 parts by weightof epoxy resin. Adding benzoxazine resin in this range allows the resincomposition to have the desired low dissipation factor (Df). If theamount of benzoxazine resin is less than 10 parts by weight, the desiredlow dissipation factor value cannot be attained; if the amount exceeds80 parts by weight, the laminate made by the resin composition will havepoor heat resistance.

The Second Hardener: Component (C) Dicyclopentadiene Phenol Resin

The resin composition of the present invention comprises from 10 to 50parts by weight of added dicyclopentadiene phenol resin based on 100parts by weight of epoxy resin. Adding dicyclopentadiene phenol resin inthis range allows the resin composition to have desired low dielectricconstant value (Dk). If the amount of dicyclopentadiene phenol resin isless than 10 parts by weight, the desired low dielectric constant valuecannot be attained and the laminate heat resistance will be lowered(T288, Tg); if the amount exceeds 50 parts by weight, the glasstransition temperature (Tg) of the laminate made by the resincomposition will be reduced.

The resin composition of the present invention preferably comprises from10 to 40 parts by weight of added dicyclopentadiene phenol resin basedon 100 parts by weight of epoxy resin.

Exclusion of Diallyl Bisphenol A (DABPA) from the Hardener Components

The hardener composition does not comprise diallyl bisphenol A (DABPA).

The inventors has discovered in previous experiments that adding diallylbisphenol A (DABPA) in epoxy resin can make the resin composition havegood crosslinking properties, increased Tg and increased peelingstrength between the resin and the copper foil.

However, through further experiments, the inventors surprisinglydiscover that, instead, removing diallyl bisphenol A (DABPA) and onlyusing dicyclopentadiene phenol resin is more helpful to improve thelaminate heat resistance (T288).

The Third Hardener: Component (D) Amine Hardener

In the resin composition of the present invention, the component (D)amine hardener is a compound comprising amino functional group,preferably a compound comprising diamino functional group. Moreparticularly, the amine hardener may be diamino diphenyl sulfone,diamino diphenyl methane, diamino diphenyl ether, diamino diphenylsulfide, and dicyandiamide (DICY) or a combination thereof. Preferably,the amine hardener may be 4,4′-diamino diphenyl sulfone, 4,4′-diaminodiphenyl methane, 4,4′-diamino diphenyl ether, 4,4′-diamino diphenylsulfide, dicyandiamide (DICY) or a combination thereof.

In an embodiment of the present invention, the amine hardener is atleast one selected from the group consisting of diamino diphenylsulfone, diamino diphenyl methane, diamino diphenyl ether, diaminodiphenyl sulfide, and dicyandiamide.

More preferably, the amine hardener is dicyandiamide (DICY).

The resin composition of the present invention comprises from 0.5 to 5parts by weight of added amine hardener based on 100 parts by weight ofepoxy resin. Adding amine hardener in this range can improve the peelingstrength between the resin composition and the copper foil. If theamount of amine hardener is less than 0.5 parts by weight, the desiredpeeling strength cannot be attained. If the amount exceeds 5 parts byweight, the hygroscopicity of the laminate made from the resincomposition will be increased, resulting in delamination and failure inlaminate PCT test (pressure cooker cooking test for copper-freelaminate).

The resin composition of the present invention preferably comprises from0.5 to 3 parts by weight of added amine hardener based on 100 parts byweight of epoxy resin.

Further, the resin composition of the present invention more preferablycomprises from 0.5 to 3 parts by weight of added dicyandiamide based on100 parts by weight of epoxy resin.

The Synergism of Three Components

The ratio of three hardeners is as follows:

(B) from 10 to 80 parts by weight of benzoxazine resin;

(C) from 10 to 50 parts by weight of dicyclopentadiene phenol resin; and

(D) from 0.5 to 5 parts by weight of amine hardener.

Thus, the ratio of three components is in turn (10-80):(10-50):(0.5-5).To obtain better synergism, the ratio of benzoxazineresin:dicyclopentadiene phenol resin:amine hardener is preferably10-60:15-35:0.5-3.

As mentioned above, the inventors discover that removing diallylbisphenol A (DABPA) and only using dicyclopentadiene phenol resinfurther improve the laminate heat resistance (T288).

Further, the present invention preferably uses the combination of thethird hardener (D) DICY with other hardeners. It is considered in theprior art that using DICY as a hardener for epoxy resin will result inlow Tg (DSC test, Tg=140° C.) and poor laminate PCT heat resistance.However, the inventors find that a better technical effect can beachieved by the synergism of the first hardener component (B)benzoxazine resin, the second hardener component (C) dicyclopentadienephenol resin and the third hardener component (D) DICY. As shown inExample E13 of the present invention, although it also attained a goodtechnical effect, the example using DDS was not better than that usingDICY. As shown in Example 7, as the amount of DICY increased, thepeeling strength also increased, and Tg met the requirement. Accordingto Comparative Example C14 and Example E14, when diallyl bisphenol A(DABPA) was removed and dicyclopentadiene phenol resin was used, theheat resistance of the copper-clad laminate (T288) was furtherincreased.

Other Components

In an embodiment of the present invention, the composition furthercomprises from 30 to 70 parts by weight of flame retardant. Said flameretardant may be selected from halogen flame retardants and also may beselected from halogen-free flame retardants.

The halogen flame retardants may be brominated flame retardants, withoutparticular limitation, which are preferably at least one selected fromthe following flame retardants: ethyl-bis(tetrabromophthalimide) (forexample, SAYTEX BT-93 commercially available from Albemarle), ethane-1,2bis(pentabromobenzene) (for example, SAYTEX 8010 commercially availablefrom Albemarle) and 2,4,6-tris(2,4,6-tribromophenoxy)-1,3,5-triazine(for example, FR-245 commercially available from ICL IndustrialCompany).

The halogen-free flame retardants may comprise nitrogen-containing flameretardants or phosphorus-containing flame retardants. The halogen-freeflame retardants may be selectively at least one compound of, but arenot limited to, the following group: bisphenol diphenyl phosphate,ammonium polyphosphate, hydroquinone-bis-(diphenyl phosphate), bisphenolA-bis-(diphenylphosphate), tris(2-carboxyethyl)phosphine (TCEP),tris(isopropylchloro)phosphate, trimethyl phosphate (TMP), dimethylmethyl phosphonate (DMMP), resorcinol bis(dixylenyl phosphate) (RDXP,such as PX-200), phosphazene (such as SPB-100), m-phenylenemethylphosphonate (PMP), melamine polyphosphate, melamine cyanurate andtri-hydroxy ethyl isocyanurate. Moreover, the halogen-free flameretardants also includes9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), phenol resin(such as DOPO-HQ, DOPO-PN, DOPO-BPN) etc., wherein DOPO-BPN may bebisphenol phenolic compounds, such as DOPO-BPAN, DOPO-BPFN, DOPO-BPSN,etc.

The resin composition of the present invention may further compriseinorganic fillers, curing accelerators, silane coupling agents,toughening agents, solvents or a combination thereof.

Adding inorganic fillers into the resin composition of the presentinvention is mainly used to increase the thermal conductivity of theresin composition and improve its characteristics, such as, thermalexpansion and mechanical strength, etc. The inorganic fillers arepreferably uniformly dispersed in the resin composition. The inorganicfiller may comprises silicon dioxide (fused, non-fused, porous orhollow), aluminum hydroxide, magnesium oxide, magnesium hydroxide,calcium carbonate, boron nitride, aluminum silicon carbide, siliconcarbide, titanium dioxide, zinc oxide, mica, boehmite (AlOOH), calcinedtalc, talc, silicon nitride, calcined kaolin. The inorganic fillers maybe in the shape of sphere, fiber, plate, granule, sheet or whisker andmay be optionally pretreated by silane coupling agent.

The resin composition of the present invention comprises from 10 to 150parts by weight of added inorganic filler based on 100 parts by weightof epoxy resin. If the amount of inorganic filler is less than 10 partsby weight, there is no significant thermal conductivity and thecharacteristics such as thermal expansion and mechanical strength arenot improved; if the amount exceeds 150 parts by weight, the flowabilityfor filling the holes of the resin composition will deteriorate and thedrill pin abrasion during the PCB drilling procedure will be increased.More particularly, the resin composition of the present inventionpreferably comprises from 30 to 70 parts by weigh of inorganic filler.

The curing accelerators of the present invention may comprise catalysts,such as Lewis acids or Lewis bases. The Lewis bases may include one ormore of imidazole, boron trifluoride amine complex, ethyltriphenylphosphonium chloride, 2-methylimidazole (2MI), 2-phenyl-1H-imidazole(2PZ), 2-ethyl-4-methylimidazole (2E4MI), triphenylphosphine (TPP) and4-dimethylaminopyridine (DMAP). The Lewis acids may include metal saltcompounds, such as the salts of manganese, iron, cobalt, nickel, copper,zinc and the like, for example, metallic catalysts such as zinccaprylate and cobalt caprylate.

The silane coupling agents of the present invention may comprise silanesand siloxanes. According to the functional groups, the silane couplingagents may be divided into amino silanes, amino siloxanes, epoxy silanesand epoxy siloxanes.

The toughening agents of the present invention are selected from theadditives comprising rubber resin, carboxy-terminated butadieneacrylonitrile rubber (CTBN), core-shell rubber, etc.

The solvents of the present invention are those selected from menthol,ethanol, ethylene glycol monomethyl ether, acetone, butanone (methylethyl ketone), methyl isobutyl ketone, cyclohexanone, toluene, xylene,methoxy ethyl acetate, ethoxy ethyl acetate, proproxy ethyl acetate,ethyl acetate, dimethyl formamide, propylene glycol methyl ether or acombination thereof.

The resin composition of the present invention may further comprise oneor a combination of the following resins: polyphenylene ether resins,cyanate ester resins, isocyanate ester resins, maleimide resins,polyester resins, styrene resins, butadiene resins, phenoxy resins,polyamide resins and polyimide resins.

Prepreg

The present invention provides a prepreg comprising the compositionaccording to the present invention.

Another object of the present invention is to disclose a prepreg thathas low dielectric constant, low dissipation factor, heat resistance andflame retardancy. Accordingly, the prepreg disclosed in the presentinvention may comprise a reinforcing material and the resin compositiondescribed above, wherein the resin composition adheres to thereinforcing material by ways of immersing, etc. and becomes a semi-curedstate upon heating at high temperature. The reinforcing material may befiber materials, woven fabrics and non-woven fabrics, such as glassfiber fabrics, which can increase the mechanical strength of theprepreg. In addition, the reinforcement may be optionally pretreated bysilane coupling agent or siloxane coupling agent, for example, the glassfiber fabrics pretreated by silane coupling agent.

Said prepreg may be cured by heating at high temperature and/or highpressure to form a cured film or a solid insulation layer and thesolvent existed in the resin composition, if any, will evaporate duringthe heating at high temperature.

Copper Clad Laminate

The present invention provides a copper clad laminate comprising thesemi-cured prepreg according to the present invention.

Another object of the present invention is to disclose a copper cladlaminate that has low dielectric property, heat resistance and flameretardancy and is particularly suitable for high speed and highfrequency signal transmission circuit board. Accordingly, the presentinvention provides a copper clad laminate comprising two or more copperfoils and at least one insulation layer, wherein the copper foils mayfurther comprise an alloy of copper with at least one metal of aluminum,nickel, platinum, silver, gold and the like; the insulation layer isformed by curing said semi-cured prepreg under high temperature and highpressure, for example, laminating said semi-cured prepreg between twocopper foils under high temperature and high pressure.

The copper clad laminate of the present invention has at least one ofthe follow advantages: low dielectric constant and low dissipationfactor, superior heat resistance and flame retardancy. The copper cladlaminate may be further processed by producing line and the like to forma circuit board. The circuit board can be operated under harshenvironment, for example, high temperature or high water absorptionresistance etc., after incorporated into electronic components withoutdeteriorating its quality.

Printed Circuit Board

The present invention provides a printed circuit board comprising thecopper clad laminate according to the present invention.

Another object of the present invention is to provide a printed circuitboard that has low dielectric property, heat resistance and flameretardancy and is particularly suitable for high speed and highfrequency signal transmission. The circuit board comprises at least onesaid copper clad laminate and the circuit board may be prepared by knownprocesses.

Unless specified, all materials of the present invention werecommercially available or prepared by conventional process in the art.Unless defined or specified otherwise, all technical and scientificterms used herein have the same meanings as commonly understood by theskilled in the art. Any methods and materials similar or equivalent tothose described herein can also be used in the process of the presentinvention.

Based on the contents disclosed herein, other aspects of the presentinvention are obvious for the skilled in the art.

Hereinafter, the present invention will be further described by way ofthe following examples. It should be understood that these examples onlyintend to describe the invention, but not to limit the scope of thepresent invention. In the following examples, for the experimentalmethods in which specific conditions were not indicated, they wereusually conducted in accordance with the national standards. If thereare no corresponding national standards, they were conducted inaccordance with common international standards, conventional conditionsor conditions suggested by the manufacturers. Unless specifiedotherwise, all parts and percentage are by weight and the molecularweight of the polymers is number average molecular weight.

Examples 1-14 and Comparative Examples 1-14

SEC-365: isocyanate-modified epoxy resin, purchased from Shin-ACorporation;

EXA-9900: naphthalene ring-containing epoxy resin, purchased fromDainippon Ink Chemicals Inc. (D.I.C.);

HP-7200H: dicyclopentadiene phenol epoxy resin, purchased from DainipponInk Chemicals Inc. (D.I.C.);

NC-3000: biphenyl epoxy resin, purchased from Nippon Kayaku Co. Ltd.;

LZ 8280: bisphenol F type benzoxazine resin, purchased from HuntsmanCorporation;

MT 35700: bisphenol A type benzoxazine resin, purchased from HuntsmanCorporation;

MT 35800: phenolphthalein type benzoxazine resin, purchased fromHuntsman Corporation;

PF-3500: diamino diphenyl ether type benzoxazine resin, purchased fromChangchun resin Corporation;

PD-9110: dicyclopentadiene phenol resin, purchased from Changchunplastics Corporation;

Dicy: dicyandiamide, purchased from Kingyorker Enterprise Co. Ltd.;

DDS: 4,4-diaminodiphenyl sulfone, purchased from Atul LTD;

SPB-100: phosphazene, purchased from Otsuka Chemical Co. Ltd.;

XZ92741: phosphorus-containing flame retardant, purchased from DowChemical Company;

PX-200: condensed phosphate, purchased from Daihachi ChemicalCorporation;

8010: ethane-1,2-bis(pentabromophenyl), purchased from AlbemarleCorporation;

BT-93: ethyl-bis(tetrabromophthalimide), purchased from AlbemarleCorporation;

Fused silica: fused silicon dioxide, purchased from Sibelco ASIA PTELTD;

2PZ: 2-phenylimidazole, purchased from SHIKOKU CHEMICALS CORPORATION;

6020: aminosilane, purchased from DOW CORNING CORPORATION.

The compositions for Examples 1-14 and Comparative examples 1-14 areshown in Table 1 and Table 2. The samples of Examples 1-14 are noted asE1 to E14 and the samples of Comparative examples are noted as C1 toC14.

The resin compositions of Examples 1-14 and Comparative examples 1-14were mixed in batches in an agitator tank and then placed into a dippingtank. The resin composition was adhered onto a glass fiber fabric bypassing the glass fiber fabric through the dipping tank, then baked tosemi-cured state to obtain a prepreg.

For one of the separately prepared prepreg, four prepregs were takenfrom the same batch and then two 18 μm copper foils were provided. Theywere laminated in the sequence of one copper foil, four prepregs and onecopper foil and then pressed in vacuum at 200° C. for 2 hours to form acopper clad laminate. The four prepregs were cured to form an insulationlayer between two copper foils.

The above copper clad laminate and the copper-free laminate afteretching away copper foil were subjected to physical propertymeasurements. The physical property measurements comprised glasstransition temperature (Tg, differential scanning calorimetry), heatresistance T-288 (copper-clad laminate test, which tested the time forheating at 288° C. without delamination; the heat resistance of thecopper-clad laminate at 288° C. was tested by Thermomechanical analysis(TMA) and evaluated by the time for heating without delamination, thelonger the better), PCT (2 atm/3 hours) (pressure cooker cooking test oncopper-free laminate, which was cooked at 121° C. for 3 hours to absorbwater, subjected to solder dip test in a solder pot at 288° C. After 20seconds, the laminate was observed whether there is delamination ornot), peeling strength between the copper foil and the laminate (testedby universal tensile machine, P/S, half ounce copper foil, the higherthe peeling strength between the copper foil and the laminate, thebetter), copper-clad laminate solder dip test (S/D, 288° C., 10 sec,heat cycles were tested), dielectric constant (Dk, the lower the better,the value of Dk of copper-free laminate was tested by AET microwavedielectric analyzer), dissipation factor (Df, the lower the better, thevalue of Df of copper-free laminate was tested by AET microwavedielectric analyzer), flaming test (UL94, V-0>V-1>V-2). The testedresults of the resin compositions of Examples 1-14 were listed in Table1 and those of Comparative Examples 1-14 were listed in Table 2.

TABLE 1 Composition E1 E2 E3 E4 E5 E6 E7 E8 E9 E10 E11 E12 E13 E14 epoxySEC-365 50 50 50 50 50 50 50 50 50 50 50 50 50 resin HP-7200H 40 NC-300060 EXA-9900 50 50 50 50 50 50 50 50 50 50 50 50 50 benzoxazine LZ8280 6015 35 35 70 10 35 35 35 35 50 resin BPF-Bz MT 35700 60 20 BPA-Bz MT35800 60 phenol- phthalein- Bz PF-3500 60 ODA-Bz Amine DICY 1 1 1 1 10.5 1 1 3 1 1 1 1 hardener DDS 1 dicyclo- PD-9110 20 20 20 20 30 30 3030 10 30 30 30 30 20 penta diene phenol resin Flame SPB-100 20 40retardant XZ92741 50 50 50 50 50 50 50 50 50 25 25 50 PX-200 25 8010 25BT-93 25 Inorganic Fused 60 60 60 60 60 60 60 60 60 60 60 60 60 80filler silica catalyst 2PZ 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.20.1 0.2 0.15 Silane 6020 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.10.1 0.4 compound solvent PM 30 30 30 30 30 30 30 30 60 30 30 30 60 MEK40 cyclo- 10 10 10 10 10 10 10 10 10 10 10 10 0 30 hexanone Propertytest Test method E1 E2 E3 E4 E5 E6 E7 E8 E9 E10 E11 E12 E13 E14 Tg DSC162 161 168 161 149 147 143 162 150 145 142 154 147 159 T288 TMA 42 4143 39 45 45 55 35 25 45 45 35 35 45 (clad) (min) S/D dipcycles >20 >20 >20 >20 >20 >20 >20 >20 >20 >20 >20 >20 >20 >20 PCT dipPASS PASS PASS PASS PASS PASS PASS PASS PASS PASS PASS PASS PASS PASS (3hr) 288° C., 20 s P/S Hoz Cu 6.5 6.3 6.0 6.7 6.3 6.0 6.3 6.3 6.8 6.1 6.16.7 6.2 6.4 foil Dk 2 GHz 4.00 4.10 4.00 4.20 4.10 4.10 4.12 4.15 4.204.10 4.10 4.10 4.20 4.05 Df 2 GHz 0.010 0.010 0.009 0.010 0.012 0.0120.012 0.009 0.012 0.011 0.009 0.009 0.013 0.009 Flame UL94 V-0 V-0 V-0V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 retardancy

TABLE 2 composition C1 C2 C3 C4 C5 C6 C7 C8 C9 C10 C11 C12 C13 C14 Epoxyresin SEC-365 50 50 50 50 50 50 50 50 50 50 50 50 50 HP-7200H 40 NC-300060 EXA-9900 50 50 50 50 50 50 50 50 50 50 50 50 50 benzoxazine LZ8280 6060 60 60 100 5 35 35 35 35 35 35 50 resin BPF-Bz Amine DICY 1 1 1 1 1 15.2 0.1 1 1 1 1 1 hardener DDS dicyclo PD-9110 20 20 30 55 30 30 30 3070 5 30 30 20 pentadiene phenol resin diallyl DABPA 10 20 10 bisphenol Aresin Flame PX-200 retardant SPB-100 40 XZ92741 50 50 50 50 50 50 50 5050 50 50 80 20 8010 BT-93 Inorganic Fused silica 60 60 60 60 60 60 60 6060 60 60 60 60 60 filler catalyst 2PZ 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.20.2 0.2 0.2 0.2 0.2 0.15 Silane 6020 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.10.1 0.1 0.1 0.1 0.4 compound solvent PM 30 30 30 30 30 30 30 30 30 30 3030 30 MEK 40 cyclohexanone 10 10 10 10 10 10 10 10 10 10 10 10 10 30Property test Test method C1 C2 C3 C4 C5 C6 C7 C8 C9 C10 C11 C12 C13 C14Tg DSC 158 151 153 151 139 162 135 159 145 136 132 137 149 155 T288 TMA(min) 18 18 18 15 50 12 35 3 30 60 20 25 25 25 S/D dipcycles >20 >20 >20 >20 >20 18 >20 15 >20 >20 >20 >20 >20 >20 PCT(3 hr)dip 288° C., 20 s Fail Fail PASS PASS PASS Fail PASS Fail PASS PASS PASSPASS PASS PASS P/S Hoz Cu foil 6.1 6 5.3 6.3 6.5 6.5 6.5 6.4 5.7 6.3 6.26.1 6.1 6.4 Dk 2 GHz 4.30 4.25 4.30 4.35 4.25 4.30 4.25 4.55 4.25 4.154.2 4.35 4.35 4.14 Df 2 GHz 0.012 0.011 0.012 0.01 0.018 0.009 0.0140.018 0.015 0.013 0.010 0.014 0.012 0.010 Flame UL94 V-0 V-0 V-0 V-0 V-0V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-1 V-0 retardancy

CONCLUSION

In Examples 1-14, using benzoxazine resin, dicyclopentadiene phenolresin and amine hardener at the same time makes the laminate meet therequirement of heat resistance (T288, Tg, S/D), water absorption andheat resistance (PCT), peeling strength (P/S) of the copper foil, lowdielectric property (Dk&Df) and flame retardancy.

As compared Example E6 with Example E7, the peeling strength (P/S) ofthe copper foil in Example E7 was increased due to the use of more DICY.

In comparative examples C1-C2, the use of diallyl biphenol A resin(DABPA) makes the heat resistance (T288) of the laminate significantlyreduced. But Example 14 without diallyl biphenol A resin (DABPA) has amuch better laminate heat resistance (T288) over Comparative exampleC14.

In comparative examples C3-C13, since the content of certain ingredientdo not fall within the scope claimed in the present invention, C3-C13 donot meet the requirement of heat resistance (T288, Tg, S/D), waterabsorption and heat resistance (PCT), peeling strength (P/S) of thecopper foil, low dielectric property (Dk&Df) and flame retardancy at thesame time.

The above examples are preferable for the present invention, but do notintend to limit the scope of the essential technical contents. Theessential technical contents were broadly defined in the claims of thepresent application. Any technical entities or methods completed byother people are also covered by the claims, if they are the same asthat defined in the claims of the present application or an equivalentmodification thereof.

All literature references cited herein are hereby incorporated byreference, just as each reference was cited independently. Moreover, itshould be understood that the skilled in the art can change or modifythe present invention based on the above disclosure and the equivalentarrangements are also included in the scope of the claims attached inthe application.

The invention claimed is:
 1. A resin composition comprising: (A) 100parts by weight of epoxy resin; (B) from 10 to 80 parts by weight ofbenzoxazine resin; (C) from 10 to 50 parts by weight ofdicyclopentadiene phenol resin; and (D) from 0.5 to 5 parts by weight ofamine hardener; wherein the resin composition is free of diallylbisphenol A (DABPA), and wherein said resin composition is capable ofpreparing a copper clad laminate having a glass transition temperature(Tg) measured by differential scanning calorimetry (DSC) greater than140° C., a dielectric constant (Dk) less than about 4.3, and adissipation factor (Df) less than about 0.013 and configured towithstand greater than 20 minutes of a heat resistance T288 capacitytest by which the laminate is tested for delamination at 288° C.
 2. Theresin composition according to claim 1, wherein the weight ratio of saidbenzoxazine resin: said dicyclopentadiene phenol resin: said aminehardener is (10-60): (15-35): (0.5-3).
 3. The resin compositionaccording to claim 1, wherein the dicyclopentadiene phenol resin isselected from the compound represented by the following structuralformula:

wherein n is a positive integer from 1 to 5, Z is selected from —H, —CH₃or a combination thereof.
 4. The resin composition according to claim 1,wherein the amine hardener is at least one selected from the groupconsisting of diamino diphenylsulfone, diamino diphenylmethane, diaminodiphenyl ether, diamino diphenyl sulfide and dicyandiamide.
 5. The resincomposition according to claim 1, wherein the epoxy resin is at leastone selected from the group consisting of bisphenol A epoxy resin,bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol AD epoxyresin, bisphenol A novolac epoxy resin, o-cresol novolac epoxy resin,trifunctional epoxy resin, tetrafunctional epoxy resin,dicyclopentadiene type epoxy resin, DOPO-containing epoxy resin,DOPO-HQ-containing epoxy resin, p-xylene epoxy resin, naphthalene typeepoxy resin, benzopyran type epoxy resin, biphenyl novolac epoxy resin,isocyanate modified epoxy resin, phenol benzaldehyde epoxy resin andphenol aralkyl novolac epoxy resin.
 6. The resin composition accordingto claim 1, wherein the benzoxazine resin is at least one selected fromthe group consisting of bisphenol A type benzoxazine resin, bisphenol Ftype benzoxazine resin, diamino diphenyl ether type benzoxazine resinand phenolphthalein type benzoxazine resin.
 7. The resin compositionaccording to claim 1, wherein the composition further comprises from 30to 70 parts by weight of flame retardant, wherein the flame retardant isat least one selected from the group of halogen-free flame retardantsand halogen flame retardants consisting of: bisphenol diphenylphosphate, ammonium polyphosphate, hydroquinone-bis-(diphenylphosphate), bisphenol A-bis-(diphenylphosphate),tris(2-carboxyethyl)phosphine, tris(isopropylchloro)phosphate, trimethylphosphate, dimethyl methyl phosphonate, resorcinol bis(dixylenylphosphate), phosphazene, m-phenylene methylphosphonate, melaminepolyphosphate, melamine cyanurate and tri-hydroxy ethyl isocyanurate,9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO),DOPO-containing phenol resin, ethyl-bis(tetrabromophthalimide),ethane-1,2 bis(pentabromobenzene) and2,4,6-tris(2,4,6-tribromophenoxy)-1,3,5-triazine.
 8. The resincomposition according to claim 1, wherein the composition furthercomprises inorganic fillers, curing accelerators, silane couplingagents, toughening agents, solvents or a combination thereof.
 9. Aprepreg made from the resin composition according to claim
 1. 10. Acopper clad laminate made from the prepreg according to claim
 9. 11. Aprinted circuit board comprising the copper clad laminate according toclaim
 10. 12. The copper clad laminate of claim 10, wherein the copperclad laminate is configured to withstand more than 20 cycles of a solderdip test (S/D) by which the laminate is tested at a temperature of 288°C. for 10 sec/cycle.
 13. The copper clad laminate of claim 10, whereinthe copper clad laminate has a peeling strength (P/S) between 6 lb/inand 6.8 lb/in.
 14. The copper clad laminate of claim 13, wherein thecopper clad laminate is configured to withstand more than 20 cycles of asolder dip test (S/D) by which the laminate is tested at a temperatureof 288° C. for 10 sec/cycle.
 15. The copper clad laminate of claim 13,wherein the copper clad laminate is configured to withstand greater than20 minutes of a heat resistance T288 capacity test by which the laminateis tested for delamination at 288° C.